Halogenated tertiary phosphite esters

ABSTRACT

Disclosed are novel halogenated tertiary phosphite esters which are the reaction product of 4,4,4-trichloro-1,2-epoxybutane or 2,4,4,4-tetrachlorobutanol with a phosphorus trihalide. These compounds are useful as flame retardant additives in plastic resin compositions.

This is a division of application Ser. No. 899,919 filed Apr. 26, 1978now U.S. Pat. No. 4,218,405.

Current and anticipated regulations restricting the flammability ofplastic wares has required the manufacturers of plastic articles toimplement effective ways to fire retard these materials. Such effortshave produced a variety of fire retardant compounds which can beincorporated into the resin mixtures. Phosphorus and halogen additivecompounds, in particular, have been found to impart favorablefire-retardancy properties.

Novel halogenated phosphite esters have now been developed, according tothe present invention, which are useful as fire retardant additives forvarious plastic compositions. These chlorinated alkyl tertiaryphosphites offer a favorable balance of cost, fire retardance, anduseful resin property modification.

The novel compounds of the present invention are addition products of4,4,4-trichloro-1,2-epoxybutane and 2,4,4,4-tetrachlorobutanol with aphosphorus trihalide.

The compound 2,4,4,4-tetrachlorobutanol (TCBA) is a well-known versatilecompound with a wide range of utilities. It can be prepared by variousconventional methods. For example, U.S. Pat. No. 3,399,217 describes amethod for preparation of TCBA by the catalyzed reaction of carbontetrachloride and allyl alcohol. TCBA reacts in a manner typical ofaliphatic alcohols, and, in addition, may be readily dehydrohalogenatedto yield the compound 4,4,4-trichloro-1,2-epoxybutane (TCBO). TCBO is awell-known reactive, high chlorine-containing epoxide useful in thepreparation of epoxy resins, lubricants, polyurethane foams, and thelike. An exemplary method for production of TCBO by dehydrohalogenationof TCBA is described in U.S. Pat. No. 3,923,844.

The chlorinated tertiary phosphites of the present invention can readilybe prepared by methods known in the art involving reaction of aphosphorus trihalide with an alkylene oxide or an alcohol (e.g., seeU.S. Pat. No. 3,810,961 and Noller, Chemistry of Organic Compounds,Third Edition (1965) page 318). Any suitable molar ratio of phosphorustrihalide to TCBO or TCBA can be employed; however, it is preferred touse stoichiometric proportions of reactants, i.e., about three moles ofTCBO or TCBA per each mole of phosphorus trihalide. More in detail, thereactions by which the present compounds can be made are represented byEquations I and II as follows: ##STR1## in which X is a halogen.

In carrying out these reactions, it is contemplated that any phosphorustrihalide may be employed; i.e., X can be chlorine, bromine, iodine orfluorine. However, it is preferred to employ those phosphorus trihalidesin which the halogen is chlorine, bromine, or mixtures thereof.Phosphorus trichloride is particularly preferred.

In addition to all TCBO or TCBA phosphate esters, derived from reactionof three moles of TCBA or TCBO per mole of phosphorus trihalide, noveltertiary phosphite esters, according to the present invention, havingone or more other constituents can also be readily prepared. Thesecompounds are represented by the formula: ##STR2## wherein X is ahalogen; n is an integer from one to three; and, each R radical isindependently selected from alkyl of 1 to about 20 carbon atoms,2-haloalkyl of about two to about eight carbon atoms, alkaryl, aryl,halogenated aryl, and arylalkyl.

These compounds are prepared by employing reactant combinations of TCBOand TCBA, as well as combinations of other alkylene oxides, alcohols,and phenols with the TCBO and TCBA. At least one or more moles of TCBOor TCBA per mole of phosphorus trihalide is used, with the remaining oneor two moles of reactant replaced with other alcohols, phenols and/orepoxides. Accordingly, aliphatic alcohols (with or without heteroatoms,such as sulfur, phosphorus, and oxygen) up to about 20 carbon atoms canbe used. These typically include methanol, ethanol, butanol,isopropanol, isobutanol, 2-methoxyethanol, TCBA, other halogenatedalcohols, and the like. Supplemental epoxides that can be used arealkylene oxides having a 1,2-epoxide ring. Illustrative are ethyleneoxide, propylene oxide, butylene oxide, pentylene oxide,epichlorohydrin, trichloropropylene oxide, trichlorobutylene oxide,TCBO, hexylene oxide, octylene oxide, and the like. Usually, theseoxides contain from two to eight, and most preferably from two to fourcarbon atoms. Further, phosphites containing alkaryl substituents can beprepared by including alkyl phenol reactants such as p-tert-butylphenol,nonyl phenol, 1,2,3 trimethyl phenol, 1,2 diethyl phenol, and otherderivatives of phenol, naphthol, cresol, BHT, and the like. Halogenatedaryl phosphite ester substituents can be accomplished through use ofhalogenated phenol reactants such as trihalo-phenol derivatives.Arylalkyl substituents can be made from reaction with arylalkyl alcoholssuch as benzyl alcohol, 2-phenyl ethanol, and other such substitutedalcohols of up to about 20 carbon atoms.

To catalyze the reaction of TCBO and TCBA, and other epoxide and alcoholreactants, with the phosphorus trihalide, tertiary amines, such aspyridine, tributylamine, triethylamine, N,N-dimethylaniline, picoline,lutidine, and the like, can be used. The use of pyridine is preferred.The amine not only serves to catalyze the reaction but also serves as ascavenger for the by-product hydrohalic acid whose presence mightotherwise initiate decomposition. In the preparation of phosphite estersfrom phosphorus trihalide and an alcohol, absence of the amine catalystusually results in cleavage of the phosphite by the hydrogen halidegenerated to produce dialkyl phosphites, phosphonates, and otherundesirable side products. It has surprisingly been discovered that inthe reaction of TCBA and phosphorus trihalide, the amine HCl scavengeris not required in order to preserve the integrity of the tertiaryphosphite.

Although the reaction may be run in the absence of a solvent, it isgenerally preferred to employ a convenient solvent medium. Any inertorganic liquid which is a solvent for both the catalyst and thephosphorus trihalide may be employed for this purpose, such as ethylenedichloride.

The novel tertiary phosphite esters of the present invention areparticularly useful as fire retardant additives for epoxy resins.

Various epoxy resins have been known in the prior art. Widely used suchresins include the glycidyl ethers which are prepared, for example, byreacting an epihalohydrin with hydroxylated compounds. In the presenceof a catalyst, these resins cure into solid materials that are commonlyused in the manufacture of coatings, molding compositions and adhesives.

In general, it is also known that the burning properties of epoxy resinscan be modified or reduced by the incorporation of chlorine therein.According to the prior art, this may be achieved by the addition of anon-reactive chlorine-containing material, e.g., chlorinated phenol anddichlorohydrin, such a material being usually combined with antimonyoxide to enhance the effect of the chlorine in reducing thecombustibility of the resin. See also Russian Pat. No. 191,021 whichdiscloses the incorporation of chlorinated polyethylene in epoxyadhesives. Alternatively, the chlorine may be chemically bound to theresin as taught in U.S. Pat. Nos. 2,839,496 and 3,496,120. The formerpatent teaches the use of1,4,5,6,7,7-hexachloro-2-(2,3-epoxypropoxymethyl)-bicyclo(2,2,1)hept-5-eneas a reactive diluent with epoxide condensation products. And U.S. Pat.No. 3,496,120 discloses the preparation of polyether epoxidecompositions by reacting together an epihalohydrin, a polyol, and achlorinated alkylene oxide such as 4,4,4-trichloro-1,2-epoxybutane. Thepolyepoxide products of such a reaction are then dehydrohalogenated toyield resinous materials which can be cross-linked into hard plasticsthat are said to be non-burning.

Any of the variety of prior art liquid, curable epoxy resins having morethan one α-epoxy group in the molecule may be used in the composition ofthe invention. However, it is generally preferred to employ the glycidylether type epoxy resins. These are generally prepared by reacting andepihalohydrin with a polyhydroxy compound in a liquid caustic medium.Such and other epoxy resins and their preparation are described indetail in H. Lee and K. Neville, Handbood of Epoxy Resins, McGraw-Hill,Inc., New York (1967). The entire disclosure of this book isincorporated herein by reference.

Illustrative glycidyl type epoxy resins include the glycidyl ethers ofbisphenols such as bisphenol-A, the glycidyl ethers of mononuclear di-and trihydric phenols, the glycidyl ethers of aliphatic polyols, theglycidyl ethers of novolac resins, and the glycidyl ethers ofpolynuclear phenols. Because of their ready commercial availability, theglycidyl ethers of bisphenol-A, are especially preferred such as may berepresented by the structural formula: ##STR3## wherein n represents anumber of one or less.

The epoxy resin composition of the invention includes a curing agent orcatalyst. Here again any such material known in the prior art to be aneffective curing agent for a particular epoxy resin as defined herein orfor any generic group of epoxy resins may be employed where feasible ordesirable. This may include two or more ingredients which act togetheras a curing system for the epoxy resin. The curing agent or system, whenmixed with the epoxy resin, serves to transform it from the liquid orthermoplastic state to a hard thermoset solid; and, depending on thenature of the particular curing agent, this transformation occurs by thecuring agent acting as a catalyst to promote the curing process, or thecuring agent may participate in a reaction with the epoxy resin therebybecoming chemically bound into the resin chain.

Illustrative epoxy resin curing agents include basic materials, such asthe Lewis bases, the inorganic bases, the primary and secondary amines,and the amides; and acidic materials such as the Lewis acids, thecarboxylic acid anhydrides, and the dibasic organic acids. These andother curing agents are described in detail in the above-cited Handbookof Epoxy Resins.

The curing agent is employed in any suitable proportion which iseffective in curing the epoxy resin. As is well known in the art, suchproportion depends largely on the chemical nature of the curing agentand on the rate of curing which is desired. Therefore, a specificproportion which is applicable in the case of one curing agent mayrepresent an insufficient or excessive level, as the case may be, when adifferent curing agent is used. Thus, the term "effective amount", asused in the specification and claims herein with reference to the curingagent, is intended to encompass any such proportion of a particularcuring agent or group of curing agents which may suitably be used tobring about curing of the epoxy resin. For general illustration,depending on the particular material used, the curing agent may beemployed in a proportion of about 4-100 parts per every 100 parts byweight of the epoxy resin.

In addition to the curing agent, if desired, other ingredients may beadded to the epoxy resin, such as taught in the prior art, in order tomodify the properties of the resin or to achieve certain objectives inconnection with its processing and commercial utilization. Thisincludes, for example, fillers, solvents or diluents, resin modifiers,and plasticizers.

Pursuant to the invention, reduced combustibility is imparted to theepoxy resin by incorporating or mixing therewith the novel tertiaryphosphite esters as defined above.

The tertiary phosphite additive may be used in any proportion which iseffective in reducing the combustibility of the epoxy resin. Forexample, such a proportion may be obtained by blending the epoxy resinwith about 1 to about 80 percent by weight, preferably about 1 to about70 percent by weight of the tertiary phosphite additive. The mostpreferred range is about 10 to about 40 percent by weight of thetertiary phosphite additive.

In preparing the epoxy composition of the invention, the tertiaryphosphite additive and the curing agent are simply added to, and mixedwith, the epoxy resin along with any other additives or diluents thatmay desirably be used. Thereafter, the mixture is allowed to cure into ahard substance. Ordinarily, such curing will take place at roomtemperature, so that elevated temperatures are not necessary. However,in practice, it is preferred to employ moderately elevated temperatures,such as about 30°-100° C., and more preferably about 40°-80° C., inorder to speed up the curing process.

Upon curing, the epoxy composition of the invention exhibits markedreduction in combustibility. As such, it can be used to advantage invarious coating, potting, casting and molding applications in whichvarying degrees of resistance to burning are required.

The tertiary phosphite esters of the present invention also areeffective as fire retardant additives for polyvinylchloride (PVC), andpolyurethane resins. These phosphite esters further are useful asplasticizers and resin stabilizers. The high chlorine content of thesephosphites results in good organic solubility, decreased watersolubility, and good effectiveness in fire retardance. The products arealso useful as functional fluids and lubricant additives.

The following examples are provided to further illustrate the invention.All parts and percentages given are by weight, unless otherwisespecified. Temperatures given are degrees centigrade.

EXAMPLE I Preparation of Tris-(1,4,4,4-Tetrachloro-2-Butyl)Phosphite

About 1 ml each TCBA (2,4,4,4-tetrachlorobutanol) and pyridine wereadded to 0.4 mole phosphorus trichloride in 100 ml of methylenechloride. A total of 1.2 moles TCBO (4,4,4-trichlorobutylene-1,2 oxide)was then added to the well-stirred solution at 20°-30° in about twohours. The reaction mixture was stirred at room temperature for aboutone hour after the addition was completed. Most of the solvent was thenremoved by warming under reduced pressure. A total of 2 ml triethylaminewas added to neutralize residual acidity. The product was then heated to60° at 1 mm for about one hour to remove residual volatiles. The natureof the phosphite product, obtained in 100% yield, was confirmed byinfrared and nuclear magnetic resonance analyses.

Calcd. for C₁₂ H₁₅ Cl₁₂ O₃ P: %Cl, 64.16; %P, 4.67; Found: %Cl, 63.88;%P, 4.80.

In a separate reaction, the addition of TCBO to phosphorus trichloridein methylene chloride without pyridine resulted in a very mildlyexothermic reaction. Subsequent work-up yielded a product withconsiderably greater viscosity than expected. This reaction apparentlyresulted in the formation of a TCBO-polymer.

EXAMPLE II Preparation of Bis-(1,4,4,4-Tetrachloro-2-Butyl)ButylPhosphite

A total of 1.2 moles TCBO was added dropwise to a solution of 0.6 molephosphorus trichloride in 250 ml carbon tetrachloride and 200 mlmethylene chloride containing about 1 ml each TCBA and pyridine. Thetemperature of the exothermic reaction was kept at 45°-52°. After thereaction was completed, another 150 ml carbon tetrachloride was added. Amixture of 0.6 mole butanol and 0.6 mole pyridine was then added to thewell-stirred solution at 15°-20°. After the reaction mixture was stirredfor 20 minutes at room temperature, the mixture was filtered free ofsalts. The solvent was removed by warming under reduced pressure.Residual volatiles were removed by heating to 50° at 2 mm for about onehour. The phosphite product, obtained in 96% yield, was treated with 2ml triethylamine to neutralize residual acidity. The nature of theproduct was confirmed by infrared spectroscopy; n(27/D) 1.5053.

Calcd. for C₁₂ H₁₉ Cl₈ O₃ P: %Cl, 53.99; %P, 5.89; Found: %Cl, 53.79;%P, 5.60.

EXAMPLE III Preparation ofBis-(1,4,4,4-Tetrachloro-2-Butyl)p-Tert-Butylphenyl Phosphite

A total of 0.5 mole p-tert-butylphenol was added portionwise to awell-stirred solution of 0.5 mole phosphorus trichloride in 100 mlcarbon tetrachloride at room temperature. The mixture was stirred for1.5 hours at room temperature after the addition was completed. Theresidual HCl by-product was expelled by heating the solution to 79°.After about 1 ml pyridine and 50 ml methylene chloride was added toabout 50°, the TCBO was added dropwise at 57°-62° over a two-hourperiod. The reaction mixture was then stored for about 18 hours at roomtemperature. Subsequent work-up was carried out as described above, theneutralized product was clarified by filtration, to give 84% yield ofproduct, n(26/D) 1.5341.

EXAMPLE IV Preparation of Tris-(2,4,4,4-Tetrachlorobutyl)Phosphite

A total of one mole TCBA was added dropwise to well-stirred 0.5 molephosphorus trichloride in the absence of solvent. The temperature of thereaction was kept at or below room temperature by the escaping HCl gas.An additional 0.5 mole TCBA was then added under reduced pressure toassist the removal of HCl. After the addition was completed, thereaction mixture was stirred for two hours under reduced pressure.Residual acidity in the product was neutralized by the addition of 1 mltriethylene. The product, obtained in 95% yield, was clarified byfiltration: n(25/D) 1.5237. Analysis by nuclear megnetic resonancespectroscopy showed the product was at least 93% tertiary phoshite.

Calcd. for C₁₂ H₁₅ Cl₁₂ O₃ P: %Cl, 64.16; %P, 4.67; Found: %Cl, 64.42;%P, 4.59.

EXAMPLE V Preparation of Bis-(2,4,4,4-Tetrachlorobutyl)Butyl Phosphite

A total of 1.2 moles TCBA was added dropwise to a well-stirred solutionof 0.6 mole phosphorus trichloride in 100 ml carbon tetrachloride. Theescaping HCl caused the reaction temperature to drop from 20° to 18°.After the addition was completed, the solution was stirred at roomtemperature for 0.5 hour. Most of the solvent and entrained HCl wasremoved by heating the solution to 50° at about 2 mm pressure. Theresidual product was redissolved in 300 ml carbon tetrachloride and wasthen treated dropwise with a mixture of 0.6 mole butanol and 0.9 molepyridine. After the mixture was post-reacted for 0.5 hour at roomtemperature, the solution was filtered free of salts. The solvent andother volatiles were removed by warming under reduced pressure to give a95% yield of product, which was further clarified by filtration with theaid of Celite: n(27/D) 1.5058. The nature of the product as a tertiaryphosphite was demonstrated by infrared spectroscopy.

Calcd. for C₁₂ H₁₉ Cl₈ O₃ P: %Cl, 53.99; %P, 5.89; Found: %Cl, 54.27;%P, 5.42.

EXAMPLE VI Preparation ofBis-(2,4,4,4-Tetrachlorobutyl)p-Tert-Butylphenyl Phosphite

The solid phenol (0.5 mole) was added portionwise to phosphorustichloride (0.5 mole) in 100 ml methylene chloride with good stirring atroom temperature. After a post-reaction for about two hours at roomtemperature, the solution was refluxed for 45 minutes. A total of onemole TCBA was then added dropwise with good stirring at roomtemperature. The escaping HCl by-product lowered the reactiontemperature so that external cooling was not required. After a 20-minutestirring at room temperature, the solution was stirred under reducedpressure at about 50° for about one hour. A final strip of volatiles at2 mm pressure gave 100% yield of colorless product. Residual acidity wasneutralized with 4 ml triethylamine; n(27/D) 1.5310. The nature of theproduct was substantiated by infrared analysis.

Calcd. for C₁₈ H₂₃ Cl₈ O₃ P: %Cl, 47.18; %P, 5.15; Found: %Cl, 47.47,%P, 5.02.

EXAMPLES VII-VIII Epoxy Resin Preparation

The phosphite additive was blended with a mixture of diglycidyl ether ofbisphenol-A (DGEBA, obtained from Shell Chemical Co. as Epon 828) and anamine curing agent (TETA, triethylene tetramine) in various proportions.The premixed epoxy resin and curing agent consisted of 12 g curing agentper 100 g resin. The phosphite-resin mixture was poured into an aluminumcup and was allowed to cure for seven days at room temperature. Themixture may be cured faster at elevated temperature. The products thusformed were hard glossy substances which often proved to be difficult toignite by flame. None of the castings showed any "bleeding" of theadditive on the surface. Test results of these epoxy compositions arereported in Table A, below.

                  TABLE A                                                         ______________________________________                                        EXAMPLE VII                                                                   Phosphite Compound 1○ (wt. %)                                                            0    10    20  30  40     50                                Shore D          85    83    86  81  68     60                                Flammability     B     B     SE  SE  SE/DNI DNI                               EXAMPLE VIII                                                                  Phosphite Compound 2○ (wt. %)                                                                 10        30         50                                Shore D                86        80         68                                Flammability           B         SE         DNI                               ______________________________________                                         1○: tris(2,4,4,4-tetrachlorobutyl) phosphite, the reaction product     of TCBA and PCl.sub.3.                                                        2○: tris(1,4,4,4-tetrachloro-2-butyl) phosphite, the reaction          product of TCBO and PCl.sub.3.                                                B: sample readily ignited by a flame and continued to burn when the flame     source was removed.                                                           SE: sample ignited with some difficulty and did not sustain a flame when      the ignition source was removed.                                              DNI: sample did not ignite during the application of a flame.            

I claim:
 1. A liquid curable epoxy composition comprising:a. an epoxyresin having more than one α-epoxy group in the molecule, b. a curingagent for said resin, and c. a halogenated tertiary phosphite esteradditive in an amount effective to reduce the combustibility of saidresin, said halogenated tertiary phosphite ester having the formula:##STR4## wherein X is a halogen; n is an integer from one to three; andeach R radical is independently selected from alkyl of 1 to about 20carbon atoms, 2-haloalkyl of about two to about eight carbon atoms,alkaryl, aryl, halogenated aryl, and arylalkyl.
 2. The composition ofclaim 1 wherein said epoxy resin is a glycidyl ether.
 3. The compositionof claim 2 wherein said proportion ranges from about 1 to about 80percent by weight.
 4. The composition of claim 3 wherein said resin is aglycidyl ether of bisphenol-A.
 5. The composition of claim 4 whereinsaid proportion is about 10 to about 40 percent by weight.
 6. Thecomposition of claim 5 wherein said halogenated phosphite ester istris-(1,4,4,4-tetrachloro-2-butyl)phosphite.
 7. The composition of claim5 wherein said halogenated phosphite ester istris-(2,4,4,4-tetrachlorobutyl)phosphite.